WO2011002084A1 - 導電粒子 - Google Patents

導電粒子 Download PDF

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Publication number
WO2011002084A1
WO2011002084A1 PCT/JP2010/061333 JP2010061333W WO2011002084A1 WO 2011002084 A1 WO2011002084 A1 WO 2011002084A1 JP 2010061333 W JP2010061333 W JP 2010061333W WO 2011002084 A1 WO2011002084 A1 WO 2011002084A1
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Prior art keywords
particles
conductive
plastic core
adsorbed
polymer electrolyte
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PCT/JP2010/061333
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English (en)
French (fr)
Japanese (ja)
Inventor
高井　健次
邦彦 赤井
憂子 永原
光晴 松沢
Original Assignee
日立化成工業株式会社
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Application filed by 日立化成工業株式会社 filed Critical 日立化成工業株式会社
Priority to CN201080029772.8A priority Critical patent/CN102474024B/zh
Priority to KR1020127001656A priority patent/KR101271814B1/ko
Publication of WO2011002084A1 publication Critical patent/WO2011002084A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
    • H01R11/01—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts characterised by the form or arrangement of the conductive interconnection between the connecting locations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to a conductive particle suitably used for an anisotropic conductive adhesive.
  • the method of mounting a liquid crystal driving IC on a glass panel for liquid crystal display can be roughly divided into two types: COG (Chip-on-Glass) mounting and COF (Chip-on-Flex) mounting.
  • COG mounting an IC for liquid crystal is directly bonded onto a glass panel using an anisotropic conductive adhesive containing conductive particles.
  • COF mounting a liquid crystal driving IC is bonded to a flexible tape having metal wiring, and these are bonded to a glass panel using an anisotropic conductive adhesive containing conductive particles.
  • Anisotropy here means conducting in the pressurizing direction and maintaining insulation in the non-pressurizing direction.
  • the gold bumps which are circuit electrodes of the liquid crystal driving IC, have been narrowed in pitch and area, so that the conductive particles of the anisotropic conductive adhesive are adjacent to each other. There may be a problem that a short circuit occurs between the electrodes. This tendency is particularly remarkable in COG mounting. Furthermore, if conductive particles flow out between adjacent circuit electrodes, the number of conductive particles trapped between the gold bumps and the glass panel decreases, resulting in an increase in connection resistance between opposing circuit electrodes, resulting in poor connection. There was also a problem.
  • Patent Documents 1 to 3 disclose conductive particles having protrusions on the surface. Further, Patent Documents 4 to 10 disclose conductive particles of a type in which the whole particles are plated after the child particles are adsorbed on the surface of the mother particles.
  • Patent Document 11 describes a type of conductive particles that form a resin film on the surface of metal particles.
  • Patent Document 12 describes a type of conductive particles in which insulation is improved by heteroaggregating resin particles having a functional group on a metal having a functional group.
  • Patent Documents 13 and 14 disclose a technique for heteroaggregating resin particles on conductive particles having protrusions as an improvement plan combining these.
  • an object of the present invention is to provide conductive particles or coated conductive particles that can obtain sufficient conductivity even when used in an anisotropic conductive adhesive for connecting a hard and smooth electrode. Is to provide.
  • the present invention relates to a conductive particle comprising a composite particle having a plastic core and non-conductive inorganic particles adsorbed on the plastic core by chemical bonding, and a metal plating layer covering the composite particle.
  • the metal plating layer has a surface that forms a protrusion.
  • Non-conductive inorganic particles are harder than the metal plating layer.
  • the conductive particles according to the present invention have sufficient conductivity even when used in an anisotropic conductive adhesive for connecting a hard and smooth electrode by having the above specific configuration. It became possible.
  • the plastic karyoplast is preferably 80 kgf / mm 2 or more 300 kgf / mm 2 or less.
  • the metal plating layer is preferably composed of nickel, palladium, gold, or a combination thereof.
  • the non-conductive inorganic particles are preferably silica particles.
  • the composite particle further includes a polymer electrolyte layer adsorbed on the plastic core, and the non-conductive inorganic particles are adsorbed on the plastic core due to a chemical bond through the polymer electrolyte layer.
  • the plastic core, the polymer electrolyte layer, and the non-conductive inorganic particles each have a functional group, and the functional group of the polymer electrolyte layer is chemically different from the functional groups of the plastic core and the non-conductive inorganic particles. It may be bonded.
  • the functional group of the polymer electrolyte layer is chemically bonded to the functional groups of the plastic core and the non-conductive inorganic particles by electrostatic interaction.
  • the functional group of the plastic core is preferably at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group, and an alkoxycarbonyl group.
  • the polymer electrolyte layer is preferably formed from polyamine.
  • the conductive particles according to the present invention preferably further comprise insulating fine particles adsorbed on the metal plating layer.
  • the present invention provides a composite particle having a plastic core and first non-conductive inorganic particles adsorbed to the plastic core by a chemical bond, a metal plating layer covering the composite particle, and a surface of the metal plating layer. It is related with the covered electroconductive particle provided with the adsorbed 2nd nonelectroconductive inorganic particle.
  • the metal plating layer has a surface that forms a protrusion.
  • the first nonconductive inorganic particles and the second nonconductive inorganic particles are harder than the metal plating layer.
  • coated conductive particles according to the present invention have sufficient insulation resistance even when used as an anisotropic conductive adhesive for connecting a hard and smooth electrode by having the above specific configuration. It was possible to obtain sufficient conductivity while maintaining.
  • the average particle size of the first non-conductive inorganic particles is preferably smaller than the average particle size of the second non-conductive inorganic particles.
  • the plastic karyoplast is preferably 80 kgf / mm 2 or more 300 kgf / mm 2 or less.
  • the composite particle further has a polymer electrolyte layer adsorbed on the plastic core, and the first non-conductive inorganic particles are adsorbed on the plastic core by a chemical bond through the polymer electrolyte layer.
  • the plastic core, the polymer electrolyte layer, and the first non-conductive inorganic particles each have a functional group
  • the functional group of the polymer electrolyte layer includes the plastic core and the first non-conductive inorganic particles. It may be chemically bonded to each functional group.
  • the functional group of the polymer electrolyte layer is chemically bonded to the functional groups of the plastic core and the first non-conductive inorganic particles by electrostatic interaction.
  • the functional group of the plastic core is preferably at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group, and an alkoxycarbonyl group.
  • a polymer electrolyte layer adsorbed on the metal plating layer is further provided, and the second non-conductive inorganic particles are adsorbed on the metal plating layer via the polymer electrolyte layer.
  • the polymer electrolyte adsorbed on the plastic core and the polymer electrolyte layer adsorbed on the metal plating layer are preferably formed from polyamine.
  • the metal plating layer is preferably composed of nickel, palladium, gold, or a combination thereof.
  • the first non-conductive inorganic particles and the second non-conductive inorganic particles are preferably silica particles.
  • conductive particles capable of obtaining sufficient conductivity even when used in an anisotropic conductive adhesive for connecting hard and smooth electrodes.
  • plating peeling of the conductive particles hardly occurs, and poor conduction due to plating peeling is effectively prevented.
  • the present invention even when used in an anisotropic conductive adhesive for connecting hard and smooth electrodes, sufficient conductivity can be obtained while maintaining sufficient insulation resistance.
  • Possible coated conductive particles are provided. Further, according to the present invention, the coating conductive particles are hardly peeled off, and the conduction failure due to the plating peeling is effectively prevented. Since not only the first non-conductive inorganic particles but also the second non-conductive inorganic particles are harder than the metal plating layer, the second non-conductive inorganic particles are more insulative than the case where the second non-conductive inorganic particles are soft. The shortage is more effectively prevented.
  • FIG. 1 is a cross-sectional view showing an embodiment of conductive particles.
  • 1 has a particulate plastic core 10 and a plurality of non-conductive inorganic particles (first non-conductive inorganic particles) 30 adsorbed on the plastic core 10 by chemical bonds.
  • the composite particle 7, the metal plating layer 20 covering the composite particle 7, and the insulating fine particles 35 adsorbed on the metal plating layer 20 are provided.
  • the insulating fine particles 35 may be non-conductive inorganic particles (second non-conductive inorganic particles).
  • the particle diameter of the coated conductive particles 1 needs to be smaller than the minimum value of the distance between the electrodes of the circuit member to be connected. Moreover, when the height of the electrode to be connected varies, it is preferable that the particle diameter of the coated conductive particle 1 is larger than the height variation. From such a viewpoint, the particle diameter of the coated conductive particles 1 is preferably 1 to 10 ⁇ m, and more preferably 2.5 to 5 ⁇ m.
  • the resin that forms the plastic core 10 is not particularly limited, but the plastic core 10 may be, for example, an acrylic resin such as polymethyl methacrylate and polymethyl acrylate, and a polyolefin resin such as polyethylene, polypropylene, polyisobutylene, and polybutadiene.
  • a resin selected from The plastic core 10 can be synthesized by a known method, and is synthesized by suspension polymerization, seed polymerization, precipitation polymerization, or dispersion polymerization.
  • the plastic core 10 is preferably spherical.
  • the plastic core 10 is preferably relatively soft. If the plastic core 10 is hard, the nonconductive inorganic particles 30 may be adsorbed, and the coated conductive particles 1 may damage the glass surface. From such a viewpoint, the compression modulus (20% K value) of the plastic core when the plastic core 10 is 20% compressed and displaced at 200 ° C. is preferably 300 kgf / mm 2 or less, and 200 kgf / mm 2. More preferably, it is as follows. If the plastic core 10 is too soft, it is difficult to measure the particle capture rate due to the indentation. Therefore, the 20% K value at 200 ° C. of the plastic core 10 is preferably 80 kgf / mm 2 or more.
  • the 20% K value of the plastic core is measured by the following method using a Fischer scope H100C (manufactured by Fischer Instrument). 1) A slide glass on which a particle sample is placed is placed on a hot plate at 200 ° C., and a weight is applied to the center direction of the particle. 2) The compressive deformation elastic modulus (K 20 , 20% K value) when the particle sample is deformed by 20% is measured according to the following formula after measurement while applying a weight of 50 mN for 50 seconds.
  • K 20 (compression deformation modulus) (3 / ⁇ 2) ⁇ F 20 ⁇ S 20 -3/2 ⁇ R -1/2 F 20 : Load (N) required to deform the particles by 20% S 20 : Deformation amount of particles at 20% deformation (m) R: radius of particle (m)
  • Non-conductive inorganic particles 30 are firmly fixed to the plastic core 10 by chemical bonding. Reflecting the shape of the non-conductive inorganic particles fixed to the plastic core 10, a protrusion 20 a is formed on the surface of the metal plating layer 20.
  • the material for forming the non-conductive inorganic particles 30 is preferably harder than the material for forming the metal plating layer 20. As a result, the conductive particles pierce the electrode during mounting, and the conductivity is improved. That is, the idea is not to harden the entire conductive particles but to harden some of the conductive particles.
  • the materials forming the non-conductive inorganic particles are silica (silicon dioxide, Mohs hardness 6-7), zirconia (Mohs hardness 8-9), alumina (Mohs hardness 9) and diamond (Mohs hardness 10). It is preferable to be selected. The value of Mohs hardness was referred to Kyoritsu Publishing Co., Ltd. Chemical Dictionary (1962).
  • the Mohs hardness of the material forming the non-conductive inorganic particles (first non-conductive inorganic particles) and insulating fine particles (second non-conductive inorganic particles) described later is the Mohs hardness of the metal forming the metal plating layer. Is more preferable, and specifically, 5 or more is preferable.
  • the difference between the Mohs hardness of the material forming the non-conductive inorganic particles and the Mohs hardness of the metal forming the metal plating layer is preferably 1.0 or more. In the case where the metal plating layer is a multilayer, a superior effect is exhibited when the non-conductive inorganic particles are harder than all the metals constituting them.
  • the first non-conductive inorganic particles 30 desirably have a hydroxyl group (—OH) on their surfaces.
  • Silica particles supplied as water-dispersed colloidal silica (SiO 2 ) with a controlled particle size are preferably used as the non-conductive inorganic particles 30 because they are easily adsorbed from the viewpoints of insulation and cost and the presence of hydroxyl groups.
  • Examples of commercially available water-dispersed colloidal silica include Snowtex, Snowtex UP (manufactured by Nissan Chemical Industries), and Quateron PL series (manufactured by Fuso Chemical Industries). In terms of insulation reliability, it is desirable that the concentration of alkali metal ions and alkaline earth metal ions in the dispersion is 100 ppm or less.
  • the inorganic oxide fine particles produced by the hydrolysis reaction of metal alkoxide, so-called sol-gel method are suitable as the non-conductive inorganic particles 30.
  • the Mohs hardness is preferably 5 or more, and more preferably 6 or more.
  • non-conductive inorganic particles 30 are used is that, if they remain as impurities, they do not cause insulation failure.
  • the metal plating layer 20 is preferably formed of nickel, palladium, gold, or a combination thereof.
  • the Mohs hardness of nickel, palladium and gold is 4.0, 4.75 and 2.5, respectively. When these combinations are employed, it is preferable to perform displacement plating of palladium or gold after nickel plating in view of the workability of plating.
  • the average particle diameter of the non-conductive inorganic particles 30 is preferably 20 to 200 nm, and more preferably 50 to 150 nm. These average particle diameters are measured by the specific surface area conversion method by the BET method or the X-ray small angle scattering method. When the average particle size of the non-conductive inorganic particles 30 is small, the conductivity improving effect tends to be small. When the average particle diameter of the non-conductive inorganic particles 30 is large, the insulation properties are lowered, and there is a tendency that the connection between the narrow pitch circuits is disadvantageous.
  • the variation coefficient (CV) of the average particle diameter of the non-conductive inorganic particles 30 is preferably 10% or less, more preferably 5% or less.
  • the non-conductive inorganic particles 30 are preferably spherical. Even after the conductive particles are formed, the measurement can be performed by the same method.
  • the variation coefficient of the size of the protrusion measured by image analysis is preferably 10% or less, and more preferably 5% or less.
  • a functional group selected from a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group and an alkoxycarbonyl group is present on the surface of the plastic core 10.
  • the nonconductive inorganic particles having a functional group such as a hydroxyl group can be firmly fixed to the plastic core.
  • acrylic acid as a copolymerization monomer when producing a plastic core
  • a plastic core having a carboxyl group on the surface can be synthesized.
  • glycidyl methacrylate as a copolymerization monomer
  • a plastic core having a glycidyl group on the surface can be synthesized.
  • the composite particles 7 may further include a polymer electrolyte layer provided between the plastic core 10 and the non-conductive inorganic particles 30.
  • the nonconductive inorganic particles 30 are adsorbed to the plastic core 10 by chemical bonding via the polymer electrolyte layer.
  • the plastic core, the polymer electrolyte layer, and the non-conductive inorganic particles each have a functional group, and the functional group of the polymer electrolyte layer is chemically different from the functional groups of the plastic core and the non-conductive inorganic particles. It may be bonded.
  • the chemical bond includes a covalent bond, a hydrogen bond, an ionic bond by electrostatic interaction, and the like.
  • the surface potential (zeta potential) of particles having a functional group selected from a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group and an alkoxycarbonyl group on the surface is usually negative when the pH is in a neutral region.
  • the surface potential of non-conductive inorganic particles having a hydroxyl group is usually negative. In many cases, it is difficult to sufficiently cover the surface of particles having a negative surface potential with particles having a negative surface potential.
  • the particles can be adsorbed on the plastic core.
  • polymer electrolyte that forms the polymer electrolyte layer a polymer that is ionized in an aqueous solution and has a charged functional group in the main chain or side chain can be used, and a polycation is preferable.
  • a polycation generally, those having a positively charged functional group such as polyamine, such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA), Polyvinylpyridine (PVP), polylysine, polyacrylamide, and a copolymer containing at least one of them can be used.
  • polyethyleneimine has a high charge density and a strong binding force.
  • the polymer electrolyte layer is made of alkali metal (Li, Na, K, Rb, Cs) ions, alkaline earth metal (Ca, Sr, Ba, Ra) ions, halide ions ( (Fluorine ion, chloride ion, bromine ion, iodine ion) are preferably substantially free of any ions.
  • alkali metal Li, Na, K, Rb, Cs
  • alkaline earth metal Ca, Sr, Ba, Ra
  • halide ions (Fluorine ion, chloride ion, bromine ion, iodine ion) are preferably substantially free of any ions.
  • the above polymer electrolyte is water-soluble and soluble in a mixed solution of water and an organic solvent.
  • the molecular weight of the polymer electrolyte cannot be generally determined depending on the type of the polymer electrolyte to be used, but is generally preferably about 500 to 200,000.
  • the coverage of the plastic core with non-conductive inorganic particles can be controlled. Specifically, when a polymer electrolyte with a high charge density such as polyethyleneimine is used, the coverage with non-conductive inorganic particles tends to be high, and a polymer electrolyte with a low charge density such as polydiallyldimethylammonium chloride is used. When used, the coverage with non-conductive inorganic particles tends to be low.
  • the coverage with non-conductive inorganic particles tends to be high, and when the molecular weight of the polymer electrolyte is small, the coverage with non-conductive inorganic particles tends to be low.
  • the polymer electrolyte By dispersing a plastic core having a functional group selected from a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group and an alkoxycarbonyl group on the surface, the polymer electrolyte is adsorbed on the surface of the plastic core.
  • a polymer electrolyte layer can be formed.
  • non-conductive inorganic particles are adsorbed mainly by electrostatic attraction. When the adsorption proceeds and the charge is neutralized, no further adsorption occurs. Accordingly, when reaching a certain saturation point, the film thickness does not increase any more.
  • the plastic core having the polymer electrolyte layer formed is taken out of the polymer electrolyte solution.
  • the rinsing is performed using, for example, water, alcohol, or acetone. Ion exchange water (so-called ultrapure water) having a specific resistance value of 18 M ⁇ ⁇ cm or more is preferably used. Since the polymer electrolyte adsorbed on the plastic core is electrostatically adsorbed on the surface of the plastic core by a chemical bond, it does not peel off in this rinsing step.
  • the polymer electrolyte solution is obtained by dissolving a polymer electrolyte in water or a mixed solvent of water and a water-soluble organic solvent.
  • water-soluble organic solvents examples include methanol, ethanol, propanol, acetone, dimethylformamide, and acetonitrile.
  • the concentration of the polymer electrolyte in the polymer electrolyte solution is generally preferably about 0.01 to 10% by mass.
  • the pH of the polymer electrolyte solution is not particularly limited. When the polymer electrolyte is used at a high concentration, the coverage of the plastic core with non-conductive inorganic particles tends to be high, and when the polymer electrolyte is used at a low concentration, the plastic core with non-conductive inorganic particles There is a tendency that the coverage ratio of becomes low.
  • the conventional hetero-aggregation method (a method in which a child particle having a functional group is brought into contact with the surface of a base material particle having a functional group) There is a possibility that a good effect cannot be obtained.
  • Non-conductive inorganic particles such as silica particles tend to be spherical when their particle sizes are the same.
  • the bond between the spherical plastic core and the spherical non-conductive inorganic particles is theoretically a point contact.
  • point contact since the bonding force is insufficient, non-conductive inorganic particles may be peeled off during plating.
  • the variation in coverage (CV) due to non-conductive inorganic particles may increase to, for example, about 40% or more.
  • the non-conductive inorganic particles are coated by alternate lamination using a polymer electrolyte, the non-conductive inorganic particles are wrapped around the polymer electrolyte, and thus the bonding force is dramatically improved. From the viewpoint of bonding strength, it is preferable to use a polymer electrolyte having a molecular weight of 10,000 or more. The binding force increases with the molecular weight, but if the molecular weight is too high, the plastic nuclei tend to aggregate.
  • the coverage of the plastic core with non-conductive inorganic particles is preferably 10 to 80%, more preferably 25 to 60%.
  • the coverage in this case can be calculated by image analysis of the central part of an SEM photograph of 100 particles. 80% is the case of close packing.
  • conductive particles having a metal plating layer having protrusions on the surface can be produced by forming a metal plating layer by a known method.
  • the metal plating layer may be a single layer or may have a laminated structure composed of a plurality of layers. In the case of a laminated structure, it is preferable that the metal plating layer has a nickel plating provided on the inner side and a gold plating layer or a palladium plating layer laminated on the outer side as an outermost layer from the viewpoint of corrosion resistance and conductivity.
  • a method for forming a metal plating layer there are methods such as substitution plating and electroplating in addition to electroless plating.
  • the metal layer may be formed by sputtering instead of plating. From the viewpoint of simplicity and cost, electroless plating is preferable.
  • the plastic core with the non-conductive inorganic particles adsorbed is dispersed in water with ultrasonic waves. Since the non-conductive inorganic particles are firmly bonded to the surface of the plastic core, the non-conductive inorganic particles are less likely to fall off by ultrasonic treatment, which is advantageous.
  • the dropout rate of the non-conductive inorganic particles is preferably 10% or less, and more preferably 3% or less, when irradiated with ultrasonic waves at a resonance frequency of 28 to 38 kHz and an ultrasonic output of 100 W for 15 minutes.
  • the plating catalyst application may be performed by a conventionally known method and is not particularly limited.
  • a plastic core with non-conductive inorganic particles adsorbed on its surface is immersed in a palladium ion solution coordinated with 2-aminopyridine, and sodium hypophosphite, sodium borohydride, dimethylamine borane, hydrazine, formalin, etc.
  • a method of reducing palladium ions to metal is reducing.
  • electroless nickel plating is performed by a known method.
  • an electroless nickel plating solution composed of sodium hypophosphite as a reducing agent is applied to a non-conductive inorganic particle that is provided with a catalyst by a building bath and a heated plating bath according to a predetermined method.
  • the thickness of the metal plating layer is preferably 10 to 300 nm.
  • the film thickness is less than 10 nm, the plating cannot follow the uneven shape, and the conductivity tends to decrease.
  • the film thickness exceeds 300 nm the entire particle becomes too hard and the possibility of damaging the glass electrode increases.
  • conductive particles having a metal plating layer having protrusions of 20 to 200 nm on the surface can be produced.
  • the coverage of the protrusions is preferably in the range of 10% to 80%, and more preferably in the range of 25 to 60%.
  • the surface should be plated with gold or palladium.
  • the thickness of the gold plating layer or palladium plating layer is preferably in the range of 10 to 50 nm.
  • the insulating fine particles (second nonconductive inorganic particles) 35 are adsorbed to partially cover the surface of the metal plating layer.
  • the insulating fine particles 35 are preferably silica particles.
  • the average particle size of the insulating fine particles 35 is preferably larger than the average particle size of the non-conductive inorganic particles 30. If the average particle size of the insulating fine particles 35 is smaller than the average particle size of the non-conductive inorganic particles, a short circuit tends to occur.
  • the average particle diameter of the insulating fine particles 35 is preferably 30 to 250 nm, and more preferably 70 to 200 nm.
  • the average particle diameter of the insulating fine particles 35 is also measured by the specific surface area conversion method by the BET method or the X-ray small angle scattering method.
  • the adsorption of the insulating fine particles may be performed by adopting an alternate lamination method through a polymer electrolyte layer, similarly to the adsorption of the non-conductive inorganic particles. It is good to form the functional group chosen from a hydroxyl group, a carboxyl group, an alkoxy group, a glycidyl group, and an alkoxycarbonyl group on the metal plating layer surface before performing alternate lamination. Subsequently, the same polymer electrolyte and treatment method as described above are employed to firmly adsorb the insulating fine particles.
  • Silicone oligomers may be attached to the surface of the coated conductive particles produced as described above. Thereby, insulation can be further improved.
  • particles having a hydroxyl group on the surface such as silica particles, are used as insulating fine particles, insulation failure tends to occur, so that adhesion of hydrophobic silicone oligomers is particularly effective.
  • FIG. 2 is a cross-sectional view showing an embodiment of a connection structure.
  • the connection structure shown in FIG. 2 has a first circuit member 60 having a driver IC 61 and a bump electrode 62 provided on the driver IC 61, and a second having a glass substrate 51 and an IZO electrode 52 provided on the glass substrate 51.
  • the circuit member 50 is connected via an anisotropic conductive adhesive 5.
  • the anisotropic conductive adhesive 5 contains a film-like insulating adhesive 3 and the above-described coated conductive particles 1 dispersed in the insulating adhesive 3.
  • the insulating adhesive 3 contains a thermosetting resin and its curing agent.
  • the insulating adhesive 3 may contain a radical reactive resin as a thermosetting resin and an organic peroxide as a curing agent, or may be an energy ray curable resin such as an ultraviolet ray.
  • thermosetting resin constituting the insulating adhesive 3 is preferably an epoxy resin, and this and the latent curing agent are suitably combined.
  • latent curing agent examples include imidazole series, hydrazide series, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide, and the like.
  • Epoxy resins include bisphenol-type epoxy resins derived from epichlorohydrin and bisphenol A, F, AD, etc., epoxy novolac resins derived from epichlorohydrin and phenol novolac or cresol novolac, and naphthalene-based epoxy resins having a skeleton containing a naphthalene ring.
  • Various epoxy compounds having two or more glycidyl groups in one molecule such as glycidylamine, glycidyl ether, biphenyl, and alicyclic can be used alone or in admixture of two or more.
  • epoxy resins it is preferable to use a high-purity product in which impurity ions (Na + , Cl- and the like), hydrolyzable chlorine and the like are reduced to 300 ppm or less, in order to prevent electromigration.
  • impurity ions Na + , Cl- and the like
  • hydrolyzable chlorine and the like are reduced to 300 ppm or less, in order to prevent electromigration.
  • the insulating adhesive 3 may contain a rubber such as a butadiene rubber, an acrylic rubber, a styrene-butadiene rubber, or a silicone rubber in order to reduce the stress after adhesion or to improve the adhesion.
  • a rubber such as a butadiene rubber, an acrylic rubber, a styrene-butadiene rubber, or a silicone rubber in order to reduce the stress after adhesion or to improve the adhesion.
  • thermoplastic resin such as a phenoxy resin, a polyester resin, or a polyamide resin
  • thermoplastic resins also have a stress relieving effect when the thermosetting resin is cured.
  • the film-forming polymer has a functional group such as a hydroxyl group.
  • the film-like anisotropic conductive adhesive 5 is, for example, a step of applying a liquid composition containing an insulating adhesive, conductive particles, and an organic solvent that dissolves or disperses these to a peelable substrate, And a step of removing the organic solvent from the applied liquid composition at a temperature equal to or lower than the activation temperature of the curing agent.
  • a liquid composition containing an insulating adhesive, conductive particles, and an organic solvent that dissolves or disperses these to a peelable substrate
  • removing the organic solvent from the applied liquid composition at a temperature equal to or lower than the activation temperature of the curing agent.
  • an aromatic hydrocarbon-based and oxygen-containing mixed solvent is preferable because the solubility of the material is improved.
  • the thickness of the film-like anisotropic conductive adhesive before connection is appropriately determined in consideration of the particle size of the coated conductive particles 1 and the characteristics of the anisotropic conductive adhesive 5, but is preferably 1 to 100 ⁇ m. If the thickness is less than 1 ⁇ m, the adhesiveness tends to decrease, and if it exceeds 100 ⁇ m, a large amount of conductive particles tend to be required to obtain conductivity. From the same viewpoint, the thickness of the anisotropic conductive adhesive is more preferably 3 to 50 ⁇ m.
  • the anisotropic conductive adhesive is not necessarily in the form of a film, and may be in the form of a paste, for example.
  • the insulating fine particles are peeled off or embedded in the electrodes at the portions where the conductive particles 1 are in contact with the electrodes, and the opposing electrodes (in the direction of arrow A) conduct.
  • insulating properties are maintained between the adjacent electrodes on the same substrate (in the direction of arrow B) by interposing insulating fine particles.
  • Example 1 Production of Conductive Particles 10 g of a plastic core body having an average particle diameter of 3.7 ⁇ m made of a copolymer of divinylbenzene and acrylic acid having an adjusted degree of crosslinking was prepared. This plastic core has a carboxyl group on its surface. The hardness of the plastic core (compression modulus when the particle diameter was displaced 20% at 200 ° C., 20% K value) was 150 kgf / mm 2 .
  • a 30% by mass polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted to 0.3% by mass with ultrapure water. 10 g of the plastic core was added to 300 mL of this 0.3% by mass polyethylene aqueous solution and stirred at room temperature for 15 minutes. The plastic core was removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the extracted plastic core was placed in 300 g of ultrapure water and stirred at room temperature for 5 minutes.
  • the plastic core is removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the plastic core on the membrane filter is washed twice with 200 g of ultrapure water to remove unimsorbed polyethyleneimine.
  • a plastic core having adsorbed polyethyleneimine was obtained.
  • a colloidal silica dispersion having an average particle diameter of 100 nm was diluted with ultrapure water to obtain a 0.33% by mass silica particle dispersion (total amount of silica: 1 g).
  • the plastic core adsorbed with polyethyleneimine was put therein and stirred at room temperature for 15 minutes. Thereafter, the plastic core was taken out by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore). Since silica was not extracted from the filtrate, it was confirmed that substantially all silica particles were adsorbed on the plastic core.
  • the plastic core with the silica particles adsorbed was placed in 200 g of ultrapure water and stirred at room temperature for 5 minutes.
  • plastic core was taken out by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the plastic core on the membrane filter was washed twice with 200 g of ultrapure water.
  • the washed plastic nuclei were dried by heating at 80 ° C. for 30 minutes and 120 ° C. for 1 hour in order to obtain plastic nuclei (composite particles) having silica particles adsorbed on the surface.
  • the composite particles whose surface was activated were immersed in distilled water and ultrasonically dispersed to obtain a suspension. While stirring this suspension at 50 ° C., nickel sulfate hexahydrate 50 g / L, sodium hypophosphite monohydrate 20 g / L, dimethylamine borane 2.5 g / L and citric acid 50 g / L were added.
  • the electroless plating solution A mixed and adjusted to pH 7.5 was gradually added to form an electroless nickel plating layer on the composite particles.
  • the thickness of nickel was adjusted by sampling and atomic absorption, and the addition of electroless plating solution A was stopped when the thickness of the nickel plating layer reached 700 mm.
  • anisotropic conductive adhesive film and connection structure sample 100 g of phenoxy resin (trade name, PKHC, manufactured by Union Carbide) and acrylic rubber (40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile) , 75 g of a copolymer of 3 parts by mass of glycidyl methacrylate, molecular weight: 850,000) was dissolved in 400 g of ethyl acetate to obtain a 30% by mass solution.
  • phenoxy resin trade name, PKHC, manufactured by Union Carbide
  • acrylic rubber 40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile
  • the conductive particles 1 were dispersed in this adhesive solution.
  • the concentration was 9% by volume based on the amount of the adhesive solution.
  • the obtained dispersion was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 ⁇ m) using a roll coater and dried by heating at 90 ° C. for 10 minutes to form an anisotropic conductive adhesive film having a thickness of 25 ⁇ m. Formed on top.
  • a chip (1.7 ⁇ 1.7 mm, thickness: 0) with gold bumps (area: 30 ⁇ 90 ⁇ m, space 10 ⁇ m, height: 15 ⁇ m, bump number 362) is used.
  • 0.5 ⁇ m) and a glass substrate with an IZO circuit were connected according to the following procedures i) to iii).
  • An anisotropic conductive adhesive film (2 ⁇ 19 mm) is attached to a glass substrate with an IZO circuit at 80 ° C. and a pressure of 0.98 MPa (10 kgf / cm 2 ).
  • the separator is peeled off, and the bumps of the chip and the glass substrate with IZO circuit are aligned.
  • the main connection is performed by heating and pressing from above the chip under the conditions of 190 ° C., 40 gf / bump, and 10 seconds.
  • Example 2 Instead of 0.33% by mass silica particle dispersion (silica total amount: 1 g), 0.53% by mass silica particle dispersion (silica total amount: 1.6 g) was used in the same manner as in Example 1, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 2 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 2, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 3 Instead of the 0.33% by mass silica particle dispersion (total amount of silica: 1 g), the same procedure as in Example 1 was performed except that the 0.42% by mass silica particle dispersion (total amount of silica: 1.27 g) was used.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 3 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 3, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 4 Instead of 0.33% by mass silica particle dispersion (total amount of silica: 1 g), 0.18% by mass silica particle dispersion (total amount of silica: 0.53 g) was used in the same manner as in Example 1, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 4 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 4, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 5 Instead of the 0.33% by mass silica particle dispersion (total amount of silica: 1 g), except that the 0.07% by mass silica particle dispersion (total amount of silica: 0.21 g) was used, the same as in Example 1, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 5 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 5, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 6 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 280 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 6 having a nickel film formed on its surface were prepared.
  • an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 7 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 100 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 7 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 7, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 8 Instead of the 0.33% by mass silica particle dispersion (total amount of silica: 1 g), the same procedure as in Example 1 was performed except that the 0.42% by mass silica particle dispersion (total amount of silica: 1.27 g) was used.
  • a plastic core (composite particle) having silica particles adsorbed on the surface and a conductive particle 8 having a nickel film formed on the surface were prepared. Furthermore, using the obtained conductive particles 8, an anisotropic conductive adhesive film and a connection structure sample were produced in the same procedure as in Example 1.
  • Example 9 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 75 kgf / mm 2 by controlling the degree of crosslinking were used as plastic nuclei.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 9 having a nickel film formed on its surface were prepared. Furthermore, using the obtained conductive particles 9, an anisotropic conductive adhesive film and a connection structure sample were produced in the same procedure as in Example 1.
  • Example 10 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 350 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle 10 having a nickel film formed on its surface were prepared.
  • an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 11 A plating solution containing 0.03 mol / L tetrasodium ethylenediaminetetraacetate, 0.04 mol / L trisodium citrate and 0.01 mol / L potassium gold cyanide and adjusted to pH 6 with sodium hydroxide was prepared. . Using this plating solution, the conductive particles 1 produced in Example 1 were subsequently subjected to gold plating treatment until the thickness reached an average of 20 nm under the condition of a liquid temperature of 60 ° C. After filtration, it was washed with 100 mL of pure water for 60 seconds to produce conductive particles 11 having a gold film with a thickness of 20 nm formed outside the nickel film. Furthermore, using the obtained conductive particles 11, an anisotropic conductive adhesive film and a connection structure sample were produced in the same procedure as in Example 1.
  • Example 12 A plating solution was prepared by adding 9 g of tetrachloropalladium, 10 g of ethylenediamine, 5 g of aminopyridine, 18 g of sodium hypophosphite, and 20 g of polyethylene glycol to 1 L of ultrapure water. Using this plating solution, palladium plating treatment was subsequently performed on the conductive particles 1 produced in Example 1 until the thickness reached an average of 20 nm under the conditions of pH 7.5 and liquid temperature of 60 ° C. After filtration, it was washed with 100 mL of pure water for 60 seconds to produce conductive particles 12 having a palladium plating film with a thickness of 20 nm formed on the outside of the nickel film. Furthermore, using the obtained conductive particles 12, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Comparative Example 1 instead of colloidal silica having an average particle size of 100 nm, acrylic resin particles having an average particle size of 100 nm were used to prepare 0.15% by mass (total amount of acrylic resin: 0.45 g). Except that this dispersion was used, a plastic core having acrylic resin particles adsorbed on the surface and a conductive particle 13 having a nickel film formed on the surface were prepared in the same manner as in Example 1. . Furthermore, using the obtained conductive particles 13, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 2 instead of colloidal silica having an average particle diameter of 100 nm, nickel particles having an average particle diameter of 100 nm were used to prepare a nickel particle dispersion liquid of 1.32% by mass (total nickel amount: 4.0 g). Except for using this dispersion, the same procedure as in Example 1 was carried out to produce a plastic core (composite particle) having nickel particles adsorbed on the surface, and to produce conductive particles 14 having a nickel film formed on the surface. Went. Furthermore, using the obtained conductive particles 14, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • Example 3 A conductive film having a nickel film was used in the same manner as in Example 1 except that a plastic core composed of divinylbenzene and an acrylic acid copolymer and having an average particle diameter of 3.7 ⁇ m was used as it was without adsorbing silica particles on the surface. Particle 15 was produced. Furthermore, using the obtained conductive particles 15, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 1.
  • the insulation resistance test and conduction resistance test were performed on the samples prepared in each example and comparative example. It is important that the anisotropic conductive adhesive film has high insulation resistance between the chip electrodes and low conduction resistance between the chip electrode / glass electrode. Ten samples of the insulation resistance between the chip electrodes were measured. The insulation resistance was subjected to an initial value and a migration test (left for 1000 hours under conditions of an air temperature of 60 ° C., a humidity of 90%, and 20 V applied), and the yield was calculated when the insulation resistance was greater than 10 9 ( ⁇ ). Moreover, the average value of 14 samples was measured regarding the conduction
  • Glass electrode cracks When there was a crack in the glass electrode even at one place, it was determined that there was a crack.
  • plating peeling When plating peeling occurred in 10% or more of the conductive particles, it was judged that plating peeling occurred.
  • Example 13 10 g of a plastic core having an average particle diameter of 3.7 ⁇ m made of a copolymer of divinylbenzene and acrylic acid having an adjusted degree of crosslinking was prepared.
  • This plastic core has a carboxyl group on its surface.
  • the hardness of the plastic core compression modulus when the particle diameter was displaced 20% at 200 ° C., 20% K value was 150 kgf / mm 2 .
  • a 30% by mass polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted to 0.3% by mass with ultrapure water. 10 g of the plastic core was added to 300 mL of this 0.3% by mass polyethylene aqueous solution and stirred at room temperature for 15 minutes. The plastic core was removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the extracted plastic core was placed in 300 g of ultrapure water and stirred at room temperature for 5 minutes.
  • the plastic core is removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the plastic core on the membrane filter is washed twice with 200 g of ultrapure water to remove unimsorbed polyethyleneimine.
  • a plastic core having adsorbed polyethyleneimine was obtained.
  • a colloidal silica dispersion having an average particle diameter of 100 nm was diluted with ultrapure water to obtain a 0.33% by mass silica particle dispersion (total amount of silica: 1 g).
  • the plastic core adsorbed with polyethyleneimine was put therein and stirred at room temperature for 15 minutes. Thereafter, the plastic core was taken out by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore). Since silica was not extracted from the filtrate, it was confirmed that substantially all silica particles were adsorbed on the plastic core.
  • the plastic core with the silica particles adsorbed was placed in 200 g of ultrapure water and stirred at room temperature for 5 minutes.
  • the plastic core was taken out by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the plastic core on the membrane filter was washed twice with 200 g of ultrapure water.
  • the washed plastic core is dried by heating at 80 ° C. for 30 minutes and 120 ° C. for 1 hour in order, and the silica core as the first non-conductive inorganic particles is adsorbed on the surface (composite) Particles).
  • the composite particles whose surface was activated were immersed in distilled water and ultrasonically dispersed to obtain a suspension. While stirring this suspension at 50 ° C., nickel sulfate hexahydrate 50 g / L, sodium hypophosphite monohydrate 20 g / L, dimethylamine borane 2.5 g / L and citric acid 50 g / L were added.
  • the electroless plating solution A mixed and adjusted to pH 7.5 was gradually added to form an electroless nickel plating layer on the composite particles.
  • the thickness of nickel was adjusted by sampling and atomic absorption, and the addition of electroless plating solution A was stopped when the thickness of the nickel plating layer reached 700 mm.
  • a 30% by mass polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted to 0.3% by mass with ultrapure water.
  • the conductive particles were added to 300 mL of this 0.3 mass% polyethylene aqueous solution, and the mixture was stirred at room temperature for 15 minutes.
  • Conductive particles were removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the extracted conductive particles were placed in 200 g of ultrapure water and stirred at room temperature for 5 minutes. Further, the conductive particles were removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the conductive particles on the membrane filter were washed twice with 200 g of ultrapure water to remove unimsorbed polyethyleneimine.
  • a colloidal silica dispersion having a diameter of 130 nm was diluted with ultrapure water to obtain a 0.1% by mass silica particle dispersion.
  • the conductive particles treated with the above polyethyleneimine were put therein and stirred at room temperature for 15 minutes.
  • Conductive particles were removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the extracted conductive particles were placed in 200 g of ultrapure water and stirred at room temperature for 5 minutes.
  • the conductive particles are removed by filtration using a ⁇ 3 ⁇ m membrane filter (Millipore), and the conductive particles on the membrane filter are washed twice with 200 g of ultrapure water to remove unadsorbed silica particles.
  • Coated conductive particles having silica particles adsorbed on the surface were obtained.
  • SC6000 manufactured by Hitachi Chemical Co., Ltd.
  • SC6000 which is a silicone oligomer having a molecular weight of 3000
  • the coated conductive particles after hydrophobization were dried by sequential heating at 80 ° C. for 30 minutes and 120 ° C. for 1 hour to obtain hydrophobic coated conductive particles.
  • the average coverage of the conductive particles by the silica particles was measured by image analysis of the SEM photograph and found to be about 28%.
  • anisotropic conductive adhesive film and connection structure sample 100 g of phenoxy resin (trade name, PKHC, manufactured by Union Carbide) and acrylic rubber (40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile) , 75 g of a copolymer of 3 parts by mass of glycidyl methacrylate, molecular weight: 850,000) was dissolved in 400 g of ethyl acetate to obtain a 30% by mass solution.
  • phenoxy resin trade name, PKHC, manufactured by Union Carbide
  • acrylic rubber 40 parts by mass of butyl acrylate, 30 parts by mass of ethyl acrylate, 30 parts by mass of acrylonitrile
  • the conductive particles 1 were dispersed in this adhesive solution.
  • the concentration was 9% by volume based on the amount of the adhesive solution.
  • the obtained dispersion was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 ⁇ m) using a roll coater and dried by heating at 90 ° C. for 10 minutes to form an anisotropic conductive adhesive film having a thickness of 25 ⁇ m. Formed on top.
  • a chip (1.7 ⁇ 1.7 mm, thickness: 0) with gold bumps (area: 30 ⁇ 90 ⁇ m, space 10 ⁇ m, height: 15 ⁇ m, bump number 362) is used.
  • 0.5 ⁇ m) and a glass substrate with an IZO circuit were connected according to the following procedures i) to iii).
  • An anisotropic conductive adhesive film (2 ⁇ 19 mm) is attached to a glass substrate with an IZO circuit at 80 ° C. and a pressure of 0.98 MPa (10 kgf / cm 2 ).
  • the separator is peeled off, and the bumps of the chip and the glass substrate with IZO circuit are aligned.
  • the main connection is performed by heating and pressing from above the chip under the conditions of 190 ° C., 40 gf / bump, and 10 seconds.
  • Example 14 Instead of 0.33% by mass silica particle dispersion (silica total amount: 1 g), 0.53% by mass silica particle dispersion (silica total amount: 1.6 g) was used in the same manner as in Example 13, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 15 Instead of 0.33% by mass silica particle dispersion (silica total amount: 1 g), 0.42% by mass silica particle dispersion (silica total amount: 1.27 g) was used in the same manner as in Example 13, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 16 Instead of 0.33% by mass silica particle dispersion (total amount of silica: 1 g), except that 0.18% by mass silica particle dispersion (total amount of silica: 0.53 g) was used, in the same manner as in Example 13, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 17 Instead of 0.33% by mass silica particle dispersion (total amount of silica: 1 g), 0.07% by mass silica particle dispersion (total amount of silica: 0.21 g) was used in the same manner as in Example 13, A plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 18 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 280 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores. Except for this, in the same manner as in Example 13, a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 19 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 100 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores. Except for this, in the same manner as in Example 13, a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 20 instead of the 0.33% by mass silica particle dispersion (silica total amount: 1 g), the same procedure as in Example 13 was performed except that a 0.05% by mass silica particle dispersion (silica total amount: 0.15 g) was used.
  • a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared.
  • the obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles.
  • an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 21 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 75 kgf / mm 2 by controlling the degree of crosslinking were used as plastic nuclei. Except for this, in the same manner as in Example 13, a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 22 Copolymer particles whose hardness (20% K value at 200 ° C.) was adjusted to 350 kgf / mm 2 by controlling the degree of crosslinking were used as plastic cores. Except for this, in the same manner as in Example 13, a plastic core (composite particle) having silica particles adsorbed on its surface and a conductive particle having a nickel film formed on its surface were prepared. The obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 23 A plating solution containing 0.03 mol / L tetrasodium ethylenediaminetetraacetate, 0.04 mol / L trisodium citrate and 0.01 mol / L potassium gold cyanide and adjusted to pH 6 with sodium hydroxide was prepared. . Using this plating solution, gold plating treatment was subsequently performed on the conductive particles having the nickel film produced in Example 13 until the thickness reached an average of 20 nm at a solution temperature of 60 ° C. After filtration, it was washed with 100 mL of pure water for 60 seconds to produce conductive particles having a 20 nm thick gold film formed outside the nickel film. Furthermore, using the obtained conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 24 A plating solution was prepared by adding 9 g of tetrachloropalladium, 10 g of ethylenediamine, 5 g of aminopyridine, 18 g of sodium hypophosphite, and 20 g of polyethylene glycol to 1 L of ultrapure water. Using this plating solution, the conductive particles having the nickel film produced in Example 13 were subsequently subjected to palladium plating treatment until the thickness reached an average of 20 nm under the conditions of pH 7.5 and liquid temperature of 60 ° C. . After filtration, it was washed with 100 mL of pure water for 60 seconds to produce conductive particles having a palladium plated film with a thickness of 20 nm formed outside the nickel film. Furthermore, using the obtained conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 5 Comparative Example 5
  • nickel particles having an average particle diameter of 100 nm were used to prepare a nickel particle dispersion liquid of 1.32% by mass (total nickel amount: 4.0 g). Except that this dispersion was used, production of plastic nuclei (composite particles) having nickel particles adsorbed on the surface and production of conductive particles having a nickel film formed on the surface were carried out in the same manner as in Example 13. went.
  • the obtained conductive particles were subjected to silica particle adsorption and hydrophobic treatment in the same procedure as in Example 13 to obtain coated conductive particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Example 6 A conductive film having a nickel film was obtained in the same manner as in Example 13 except that a plastic core composed of divinylbenzene and an acrylic acid copolymer and having an average particle diameter of 3.7 ⁇ m was used as it was without adsorbing silica particles on the surface. Particles were made. Furthermore, using the obtained conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • Coated conductive particles were obtained in the same manner as in Example 13 except that instead of the ⁇ 130 nm colloidal silica dispersion, the ⁇ 130 nm acrylic resin particle dispersion was used to coat the conductive particles with acrylic resin particles. Furthermore, using the obtained coated conductive particles, an anisotropic conductive adhesive film and a connection structure sample were prepared in the same procedure as in Example 13.
  • the insulation resistance test and conduction resistance test were performed on the samples prepared in each example and comparative example. It is important that the anisotropic conductive adhesive film has high insulation resistance between the chip electrodes and low conduction resistance between the chip electrode / glass electrode. Ten samples of the insulation resistance between the chip electrodes were measured. The insulation resistance was subjected to an initial value and a migration test (left for 1000 hours under conditions of an air temperature of 60 ° C., a humidity of 90%, and 20 V applied), and the yield was calculated when the insulation resistance was greater than 10 9 ( ⁇ ). Moreover, the average value of 14 samples was measured regarding the conduction
  • Glass electrode cracks When there was a crack in the glass electrode even at one place, it was determined that there was a crack.
  • Table 4 shows the measurement results. Both examples achieved good initial conductivity with sufficient insulation resistance. This is presumably because the hard silica particles pressed the nickel layer protrusions against the IZO electrode, and the nickel protrusions pierced the hard IZO electrode, thereby increasing the conductivity. Examples 23 and 24 provided with a gold plating layer or a palladium plating layer also showed good characteristics. In Comparative Example 8 in which acrylic resin particles are used as the second non-conductive inorganic particles covering the conductive particles, the acrylic resin particles are deformed by the pressure of the plating protrusion, and the insulation and conductivity are inferior to those of Example 13. It is thought that it became a thing.
  • SYMBOLS 1 Coated conductive particle (conductive particle), 3 ... Insulating adhesive, 5 ... Anisotropic conductive adhesive, 7 ... Composite particle, 10 ... Plastic core, 20 ... Metal plating layer, 20a ... Projection part, 30 ... Non-conductive inorganic particles (first non-conductive inorganic particles), 35 ... insulating fine particles (second non-conductive inorganic particles), 51 ... glass substrate, 52 ... IZO electrode, 61 ... driver IC, 62 ... bump electrode.

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CN103748637A (zh) * 2012-01-19 2014-04-23 积水化学工业株式会社 导电性粒子、导电材料及连接结构体
JP2016222770A (ja) * 2015-05-28 2016-12-28 旭化成株式会社 複合粒子及びこれを含有する水性分散液

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